Cellulosic article of manufacture and method for preparing same



Patented Nov. 16, v

UNITED STATE PATENT orrlca CELLULOSIC ARTICLE OF MANUFACTURE AND METHOD FOR PREPARING SAME Daniel E. Strain, Wilmington, Del., assignor, by mesne assignments, to E. I..du Pont de Neinours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application September 28, 1934,

Serial No. 745,976

2 Claims.

This invention relates to cellulosic structures such as filaments, threads, fabrics, sheets, films,

caps, tubing, or the like. More particularly, this invention relates to cellulosic structures of the type just mentioned having a subdued or low luster and/or that are more or less opaque.

In the ordinary methods of preparing cellulosic structures, suchas filaments, threads, films, caps,

tubing, etc., from viscose, cuprammonium, nitrocellulose, cellulose acetate and other cellulosic solutions (without the addition of opaquing and/or low luster-inducing agents to the solutions), the products are transparent or translucent and/or very highly lustrous. For many purposes,

' transparency, brilliant, sheen and luster are not desirable and thus restrict the uses of the materials. Recently, various methods have been proposed for producing cellulosic structures having a low or subdued luster and/ or opacity.

. I have found that I can produce cellulosic structures characterized by a low luster and/ or opacity by incorporating therein an organic ester of the character'described in detail hereinafter which imparts opacity and/orlow luster by remaining in the cellulosic structure.

An object of the invention comprises the production of new opacified and/or low luster cellulosic structures. A further object of the invention relates to the production of novel cellulosic structures containing organic compounds which remain in the finished article and which impart opacity and/or low luster." Other objects of the invention will appear hereinafter.

The objects of the invention are accomplished in general by incorporating in the cellulosic solution from which the structure is to be produced an opaquing and/or a low luster-inducing agent be considered a nucleus. Thus, benzene, naphthalene and carbazole have one, two, and three nuclei respectively.

These opaquing and/or low luster-inducing agents, which are preferably white in color,

possess a sufliciently low vapor pressure and are sufficiently inert to resist the change or removal from the cellulosic structure in the ordinary process of making and finishing the same during'the manufacture thereof. They also effectively resist removal or change during any of the usual processes to which the finished cellulosic structure may be subjected, such as boiling-off, dyeing, bleaching, washing,ironing, etc. 'These sub stances are incompatible with the mass .of the substance constituting the final product. They may be soluble but, in the preferred embodiment of this invention, they are insoluble in the solution from which the structure is prepared.

4 Highly effective delusterants function in particular by reason of their opacifying power which is a. function of the difference in refractive index between the delusterant particle and the surrounding medium. Those in my preferred range difier from the index of thev medium by at least 0.l0 and.the greater this difference, the more effective the compound as an opacifier and/or delusterant. Most organic compounds have several indexes and the statement just made refers to the highest index of the compound or to any one of the several indexes- It is furthermore of importance that the ester ifying conditions such as the presence of 6% caustic at ordinary temperatures.

The esters considered as being within the scope of this invention may be prepared from various types. of acids and alcohols, among which may be named the following j 1. Types of acids: v

(a) Monobasic and polybasic carboxylic and .has a high degree of chemical stability to saponw thiocarboxylic acids, including aliphatic, alicyclic, aromatic and heterocyelic. (b) Sulfonic, sulfinic and phosphonic acids. including aliphatic, alicyclic, aromatic and heterocyclic. (c) Strictly inorganic acids such as carbonic and phosphoric. 1

2. Types of alcohols, mono and polyhydrlc':

(a) Aliphatic and alicyclic alcohols or sub-' stituted'byaromatic or heterocyclic groups. (b) Aromatic and heterocyclic alcohols including those substituted by or joined may be an alkyl, aryl or alkaryl, or

similar group.

As illustrative examples of organic esters coming within the scope of the present invention the following I may be mentioned:

1,1'-binaphthy1 2,2-dibntyrate Di-betamaphthyl succinate 5 to it 0-0 C-GHaCHy-U o-om 1,1'-binaphthyl 2,2'-dibenzoate Di-biphanyl am: in mhmhydro phthalic acid Dl-dpha-naphthyl phtlnkto 1, 1'-dimphthylmethane 8, 3'-dibenzoata 1, l-dinaphthyimethnne a, B'dibenzunesuiionaia I to, to,

Beta-naphthyl ester 0! nanhthofumne-l-earboxyiic acid Dl-biphenyl ester of biphenylphosphonic acid Tri-blphanyl phosphate m-beu-m ntim carbonate Dl-alpha-mphthylmethyl phthalate V Di-benzoate of 8,5 hydroxyphenyl-phenyl sulfone Di-benzoate. of 4 benzoylamino-IL3-dihydrory benzene I Dltortiary butyl ester of l,l-bi(2-naphthoxyacetic acid) H: CH:

Organic compounds'of the character described which have a relatively high index of refraction and which are preferred on the basis of cost, color stability, acid insolubility and efiectiveness are the following: Di-naphthylmethane-dibenzene sulfonate, di-beta-naphthyl succinate, di-naphthylmethane-di-acetate, di-naphthylmethane-dibenzoate, di-beta-naphthyl butyrate, and dibeta-naphthyl carbonate.

The quantity of the low luster-inducing and/or opaquing agent which may be used may vary within wide limits, depending principally upon the opaquing and luster desired in the final product; Cellulosic structures containing these low luster-inducing and/or opaquing agents in amounts ranging from 0.10-20.0% by weight have given satisfactory results, but, of course, it is obvious that smaller or larger quantities may be employed as desired. When a viscose solution is employed, satisfactory results may be secured if it contains 7% cellulose and from 0.01-1.5% more or less of the low luster-inducing and/or opaquing agent. i

If desired, the lowluster-inducing agents con-- templated by the instantv invention may be used in combination with each other and/or with other low luster-inducing agents, such as mineral oil, petroleum jelly, waxes, paraflin, benzene, toluene, pine oil or inorganic pigments, such as titanium oxide, lithopone, zinc sulfide, etc.

The low. luster-induc 1g agent maybe added to the solution at, any stage in the course of the manufacture thereof, or after the preparation of the solution and prion'to the spinning, extrusion or casting operation. It may be added directly, if the particle size is satisfactory, or after suitable adjustment of the particle size by any of the well known methods, such as emulsification, grinding in a colloid mill or pebble mill, or in the form of a suspension or emulsion prepared ,with or without the assistance of suitable dispersing agents or protective colloids, such as soaps, sulfonated oils, alkyl naphthalene sulfonates, sodium caseinate, etc. or combinations thereof.

In order to more fully explain the principles Y of this invention, the following illustrative exable opacity and low luster, far superior to that obtained with mineral oil and similar to that obtained with inorganic pigments.

Example 1I.-A sample of 1,1-dina'phthylmethane-3,3'-di-acetate is ground, incorporated in viscose, and spun in the manner described in Example I. The resulting product has a desirable opacity and low luster.. 1 Example III.--A sample of di-beta-naphthy succinate is ground, incorporated in viscose and spun in the same manner described in Example I. The resulting product has a desirable opacity and aw luster. v

It is to be understood that these examples'do not in any way restrict the invention thereto but merely illustrate several specific and preferred embodiments which have given satisfactory results.

Though the preferred embodiments of this invention contemplate the incorporation of the low luster-inducing agent in the solution at some time prior to the extrusion or casting thereof, satisfactory results may be secured also by applying the low luster-inducing agent to a previously formed cellulosic structure. In other words, the low luster-inducing agent may be incorporated in the final cellulosic structure by an after-treatment.

Though the invention has been specifically described in connection with the viscose process, it

v is obvious that the principles thereof are equally low luster-inducing substance be insoluble in the solvent employed. However, resinous materials and certain crystallized substances soluble in the solvent, precipitate, on the evaporation of the solvent, in the cellulose acetate in the form of fine amorphous or crystalline particles sufilcient- Iy small and well distributed to avoid harmful efiect on the physical properties of the resulting structure. The advantage in such cases lies in avoiding the'necessity for emulsifying or'grinding the compounds to obtain suitable subdivision. Suitable compounds may be readily selected from any specific system by one skilled in the art.

While the invention has been described generally with respect to the use of the various compounds mentioned herein in opaquing cellulosic structures prepared by casting and/or spinning methods, it is desired to emphasize the fact that these compounds are of special benefit in the spinning of artificial silk. Thus, undelustered artificial silk has a shade and luster which is undesired ior a great many purposes. In accordance with the present invention, it is possible to produce artificial silk, particularly of the regemerated cellulose type prepared from viscose or cuprammonium cellulose, having a pleasing dull appearance, the dullness being of any degree desired, in which the opaquing and/or delustering 40 agent is uniformly distributed and which does not interfere with the tenacity of the yarn to any large extent.

Since it is obvious that various changes and modifications may be made in the above description without departing from the nature or spirit thereof, this invention is not restricted thereto except as set forth in the claims.

I claim:

1. A cellulosic structure containing a finely divided delustering agent taken irom the group consisting of 1,1-binaphthyl 2,2'-dibutyrate, dibeta-naphthyl. succinate, 1,1-binaphthyl 2,2- dibenzoate, di-biphenyl ester oi. trans-hexahydro phthalic acid, dialpha-naphthyl phthalate, 1,1- dinaphthylmethane 3,3 dibenzoate, 1,1 dinaphthylmethane 3,3'-dibenzenesuliouate, betanaphthyl ester of naphthofurane-l-carboxylic acid, di-biphenyl ester 01 biphenylphosphonic acid, tri-biphenyl phosphate, tri-beta-naphthylphosphate, dHbeta-naphthyl carbonate,;di-ialpha-naphthylmethyl phthalate, di-benmate of 3,5 hydroxyphenyl-phenyi sulfone, di-benzoate of 4 benzoylan ino-1,3-dihydroxy benzene, di-

beta-naphthoate of 4-beta-naphthoyl amino-1,3- dihydroxy benzene, ditertiary butyl ester of 1,1- bi(2-naphthoxyao etic acid) 2. An artificial thread having low luster imparted, thereto by the incorporation therein 01 a finely divided delustering agent taken from the group consisting of 1, 1'-binaphthy1 2,2'-dibutyrate, di-beta-naphthyl succinate, 1,1-binaphthyl 2,2'-dibenzoate, di-biphenyl ester of trans-hexahydro phthalic acid, di-alpha-naphthyl phthalate, 1,1 dinaphthylmethane 3,3 dibenzoate, 1,1 dinaphth-ylmethane 3,3 dibenzenesulfonate, beta-naphthyl ester of naphthoiurane-lcarboxylic acid, di-biphenyl ester of biphenylphosphonic acid, tri-biphenyl phosphate, tribeta-naphthylphosphate, di-beta-naphthyl carbonate, di-alpha-naphthylmethyl phthalate, dibenzoate of 3,5 hydroxyphenyl-phenyl sulione,

di-benzoate of 4 benzoylamino- 1,3 -dihydroxy benzene, di-beta-naphthoate oi 4-beta-naphthoyl amino-1,3-dihydroxy benzene, ditertiary butyl ester of 1,1'-bi(2-naphthoxyacetic acid).

DANIELE. 8mm, 

